Benzyloxy compounds

ABSTRACT

NOVEL ORGANIC COMPOUNDS ARE FORMED BY TREATING A MIXTURE OF ALLYLIC HALIDES WITH AN ALKALI METAL SALT OF BENZYL ALCOHOL. THE REACTION PRODUCTS ARE OXIDIZED TO FORM NOVEL EPOXIDE COMPOUNDS. THE NOVEL BENZOYLOXY COMPOUNDS ARE USEFUL AS MONOMERS FOR POLYMERIZATION REACTIONS AND THE EPOXY DERIVATIVES THEREOF ARE USEFUL IN PREPARING CURING AGENTS, ADHESIVES, AND PLASTICIZERS.

3,658,915 BENZYLOXY COMPOUNDS Raymond L. Cobb, Bartlesville,Okla.,assignor to Phillips Petroleum Company No Drawing. Application Oct. 17,1968, Ser. No. 768,520,

now Patent No. 3,527,773, dated Sept. 8,1970, which is acontinuation-in-part of application Ser. No. 531,351, Mar. 6, 1966.Divided and this application May 12, 1970, Ser. No. 36.693

Int. Cl. C07c 43/20 US. Cl. 260-611 A ABSTRACT OF DISCLOSURE Novelorganic compounds are formed by treating a mixture of allylic halideswith an alkali metal salt of benzyl alcohol. The reaction products areoxidized to form novel epoxide compounds. The novel benzoyloxy compoundsare useful as monomers for polymerization reactions and the epoxyderivatives thereof are useful in preparing curing agents, adhesives,and plasticizers.

This application is a division of copending application Ser. No. 768,520filed Oct. 17, 1968 and now Patent No. 3,527,773, which is acontinuation-in-part of application Ser. No. 531,351, filed Mar. 6,1966, now abandoned.

This invention relates to the production of novel organic compounds. Inone aspect, this invention relates to novel organic derivatives ofallylic halides. In another Claims aspect, this invention relates tonovel epoxide derivatives of said allylic halides.

I have discovered that if a mixture of allylic halides is formed byhalogenating olefins in the presence of excess halogen and this mixtureis subsequently treated with an alkali metal salt of benzyl alcohol thatnovel compounds are produced which can be readily separated by fractionation, crystallizaation, and the like. Ihave further discovered that itis possible to treat these novel reaction products with peroxidizingagents in order to form novel epoxide derivatives thereof. This mixture,of halogenated allylic halides, can be characterized as containingcompounds having the following formulas:

where each R is selected from the group consisting of hydrogen and analkyl radical having 1 to, 4 carbon atoms and each X is selected fromthe group consisting of chlorine, bromine, and iodine.

- Some specific examples of such halogenated ..allylic halides are1,3-dichloro-2-methylpropene; 3-chloro-2-(chloromethyl) propene;l-bromo-2- (bromoethyl) butene; 3-bromo-2- (bromomethyl)butene-1;1-iodo-2-( 1-iodopentyl)-heptene-1; l,1-bis( l-iodopentyl) ethylene;1-chloro-2-(chloromethyl)hexene-1; 3-chloro-2v- (chloromethyl) hexene-l;1-bromo-2-( 1-bromopropyl)pentene-1 1,1-bis-( l-bromopropyl ethylene; H.1-chloro-3-bromo-2-methylpropene; 3-bromo-2- (chloromethyl) -propene;and the likean d mixtures thereof.

1, 1-'b1s(bnzyloxymethyl) ethylene;

3,658,915 Patented Apr. 25, 1972 ICC :r I z M is an alkali metal. Theinitial halogenation of an olefin can be carried out in the presence ofcarbon tetrachloride. The step of reacting the halogenated mixture withan alkali metal salt of benzyl alcohol is carried out in the presence ofa solvent which is nonreactive under the conditions of the reaction.Such solvents are benzene, toluene, ethylbenzene, tetrahydrofuran,cyclohexane, parafiin hydrocarbons boiling at a temperature of 70-150 0;ethers such as bismethoxyethyl ether, dioxane and mixtures of 2 or moreof such compounds. It is also within the scope of this invention tocarry out this reaction in the absence of an extraneous solvent ifexcess benzyl alcohol is employed.

Some specific examples of such benzyloxy products are:

1 chloro- 2-methyl-3 -benzyloxypropene;

1-bromo-2-(benzyloxymethyl)butene; 3 -benzyloxy-2- (benzyloxymethyl)butene-l 1-iodo-2-( l-benzyloxypentyl heptenel;1,1-bis(l-benzyloxypentyl)ethylene;

1-chloro-2- benzyloxymethyl hexene-l 3 -b enzyloxy-2- (benzyloxymethylhexene- 1 I-bromo- Z- (,l-benzyloxypropyl) pentene- 1 1,1-bis(lvbenzyloxypropyl) ethylene; l-chloro-3-benzyloxy-Z-methylpropene;

and the like and mixtures thereof. a The products I and II can betreated with a suitable oxidizing agent for conversion to novel epoxideshaving the following structures:

wherein R and X are as defined hereinabove.

Oxidizing agents which are useful in oxidizing the novel allylic halidesto the corresponding epoxides are selected from the group consisting ofperbenzoic acid and substituted perbenzoic acids such asm-chloroperbenzoic acid, persulfates such as sodium persulfates,peroxides such as hydrogen peroxide, peracetic acid and other suchperoxidic oxidizing agents.

The epoxidation reaction can be carried out in the presence of a solventselected from the group enumerated hereinabove in regard to the step ofreacting the novel allylic halogenated compounds with a metal salt ofbenzyl alcohol.

Some specific examples of such epoxides are:

1-chloro-2-methyl-3-benzyloxy-1,2-epoxypropane;

1, l-bis (benzyloxymethyl )ethylene oxide;1-bromo-2-(benzyloxymethyl)-1,2-epoxybutane;3-benzyloxy-2-(benzyloxymethyl)-1,2-epoxybutane; 1-iodo-2-(l-benzyloxypenyl)-1,2-epoxyheptane;

1', l-bis( l-benzyloxypentyl) -ethylene oxide; 1-chloro-2-(benzyloxymethyl)-1,2-epoxyhexane; 3-benzyloxy-2-(benzyloxymethyl)-1,2-epoxyhexane; l-bromo-2-( l-benzyloxypropyl) l ,2-epoxypentane; 1,l-bis( l-benzyloxypropyl)ethylene oxide;1-chloro-3-benzyloxy-2-methyl-1,2-epoxypropane and the like and mixturesthereof.

The novel compounds having Formula I or II are useful as monomersforpolymerization reactions because of the olefinic structure which theyretain. In addition, the epoxy derivatives thereof are useful inpreparing curing agents,

Product 2: l-chloro-2-rnethyl-3-benzyloxypropene (II),

- (C H CIO;M.W. 196.68) 218 g. (1.1 mols).

adhesives, and as plasticizers in various compositions. Specificaily,these novel epoxy derivatives can be used as plasticizers for poly(vinylchloride). 1

This invention, for the sake of clearness and understanding, will beillustrated and discussed in connection with its specific application tothe production of chlorinated methallyl chloride and to the subsequentbenzylation and epoxidation thereof.

EXAMPLE I Five hundred grams (5.5 mols) of methallyl chloride werereacted with 520 grams of chlorine (7.3 mols) in the presence of 500 ml.of carbon tetrachloride. The chlorine was passed through a stirredreactor containing the'methallyl chloride and the carbon tetrachlorideat room temperature. HCl gas was evolved. The resulting solution waswashed four times with water and once with sodium bicarbonate solutionto remove HCl, and then dried over calcium chloride. This product wasdistilled in a 6-inch Vigreux column at atmospheric pressure over asteam bath maintained at 98 C. The residue from this fractionation wasdistilled in an 1.8-inch column packed with glass helices at 160 mm. Hgpressure and employing a 5/1 reflux ratio. A mixture ofS-chloro-Z-(chloromethyl)propene and 1,3- dichloro-Z-methylpropene wasobtained in the first fraction. This was used in the reaction describedunder Example II.

., EXAMPLE 11-1..

Five hundred milliliters (5 mols) of benzyl alcohol were placed in astirred reactor and heated on a steam bath maintained at 98 C. Smallpieces of sodium metal were added to the flask gradually until 80 grams(3.5 mols) had been added. At the end of the sodium addition, themixture had nearly gelled. Five hundred milliliters of tetrahydrofuranwas then added as solvent and 230"grams of the mixture of chlorinated.methallyl chloride obtained in 7 Example I was added through a droppingfunnel. Stirring and heating of the mixture was continued for anothertwo hours. A vigorous reaction took place. The mixture was stirred underreflux for another hour at which time it was substantially gelled.Heating without stirring was continued for another hour. The gel wasbroken by addition of 1000 ml. of H 0, and two liquid phases consistingof an aqueous phase and an organic phase formed. The aqueous phase wasseparated from the organic phase and the organic phase was washed twicewith water'and once with c, sass; 7.5 1,.

Boiling pt. 92 C./ 1 mm. Hg; n -1.524l. Analysis-Calculated (percent):C, 67.18; H, 6.66; CI, 18.03. Found (percent): C, 67.3; H, 6.7; Cl,18.1.

The structure of the ethers was confirmed by NMR analy EXAMPLE ,III

' Ninety-four grams (0.35 mol) of 1,1-bis(benzyloxymethyUethyIene wasdissolved in ml. of benzene in a stirred flask. Then91 grains (0.35 mol)of m-chloroperbenzoic acid was dissolved in 850 ml. of benzene and wasslowly added to the stirred flask at room temperature over a' 3 /2 hourperiod. After 2% hours a white solid formed. Stirring was continuedovernight. The mixture was filtered and the white solid washed withbenzene. The filtrate was washed twice with dilute aqueous sodiumcarbonate (5 percent), once with water, and dried over anhydrous sodiumsulfate. Then the benzene was removed under an aspirator vacuumdistillation to leave about 100 grams of an oil. The product wasidentified as 1,l-bis(benzyloxymethyl) ethylene oxide and had thefollowing analysis:

Product3: C H 0 M.W. 284.36.

Analysis.Calculated (percent): C, 76.03; H, 7.09; O (Oxirane), 5.63.Found (percent): C, 76.0; H, 7.1; O (Oxirane), 5.41.

I .Boiling pt. l56l63 /0.1 mm. Hg; 71 -15450.

A similar run was carried out and this gave 79.5 g. (80 percent yield)of product which boiled at -187 C. at 0.8 mm. Hg; n -1.5454.

The structure of the above compounds, both the novel halogenated allylichalide derivatives and also the novel epoxy compounds were proven bynuclear magnetic resonance analysis. The nuclear magnetic resonance dataindicated that these samples have the following structures:

Sample The following assignments were used in formulating thesestructures:

Chemical shift position (tau) The following integral measurements weremade from the spectra:

a a s a s 'a a Sample Ha H b He 1111 He H! H0 HI:

5 EXAMPLE IV Samples having the following formulations were blended andmilled at 320 F. and then pressed into sheets of 75 mil thickness at 340F.

Constituent A B C Pol Vin l chloride 100 100 1 DO S UZ 51 4s 4smenisci-90 6 1,1-b s(benzyloxymethyl) ethylene oxide- 6 Mark M 2 2 2Stearic acid 0. 5 0. 5 5

h Agiounts of constituents are given in parts per 100 parts of polyv y eor e.

Dioctyl phthalate, a conventional plastieizer for polyvinylchioride.

3 An epoxy tallate ester marketed by Food Machine Corporation havgzdamolecular weight comparable to 1,1-bis(benzyloxymethyl)ethylene o e.

4 An organic Ba-Cd stabilizer of the phenate type containing a chelatormarketed by Argus Chemical Company.

The above samples had the following physical properties:

SAMPLE A B (J Tensile at break, p.s.i 2, 733 2,653 2, 770 Elongation atbreak, percent 363 397 397 100% modulus, p.s.i 1,467 1,384 1, 335

While this invention has been described in a detailed manner andillustrated with particular reference to the chloride derivatives ofmethallyl chloride, it is to be understood that modifications may bemade and that no limitations other than those imposed by the scope ofthe appended claims is intended.

I claim:

1. Organic compounds selected from the group of compounds characterizedby the following formulas:

R CuH OH2OC CalLCHgO C wherein R is selected from the group consistingof hydrogen and alkyl radicals having 1 to 4 carbon atoms and X isselected from the group consisting of chlorine, bromine and iodine.

2. In accordance with claim 1, a compound identified as1,l-bis(benzyloxymethyl)ethylene.

3. In accordance with claim 1, a compound identified as1-chloro-2-methyl-3-benzyloxypropene.

4. In accordance with claim 1, a compound identified as1,1-bis(1-benzy1oxyethyl)ethylene.

References Cited UNITED STATES PATENTS 2,153,513 4/1939 Coleman et a1.260-611 A X 2,541,091 2/ 1951 Oroshnik 260-4511 A X 2,847,477 8/1958Watanabe et a1. 260-611 A 2,847,478 8/1958 Hwa et a1. 260611 A BERNARDHELFIN, Primary Examiner

